Transport and mechanical behavior in PEO-LLZO composite electrolytes

Kim, Hong-Keun; Barai, Pallab; Chavan, Kanchan; Srinivasan, Venkat

doi:10.1007/s10008-022-05231-w

Transport and mechanical behavior in PEO-LLZO composite electrolytes

Journal Article · Mon Jul 25 00:00:00 EDT 2022 · Journal of Solid State Electrochemistry

DOI:https://doi.org/10.1007/s10008-022-05231-w· OSTI ID:1877696

Kim, Hong-Keun; Barai, Pallab; Chavan, Kanchan;

Abstract

Composite solid electrolytes (CEs), wherein ion-conducting polymer and ceramic/glass is mixed, are promising candidates for all-solid-state batteries due to their promise of acceptable ionic conductivity and mechanical properties compared to their individual constituents. While numerous studies have focused on improving the performance of CEs, it is still unclear what the material targets are that can result in improved macroscopic performance especially in light of the coupled needs for high transport and high mechanical strength in these materials. In this study, a two-dimensional (2D) mathematical model is developed to investigate electrochemical and mechanical characteristics of CEs. The model is compared to CEs consisting of poly-ethylene-oxide (PEO) polymer and lithium lanthanum zirconium oxide (LLZO) ceramic material with examination of the impact of varying LLZO volume fractions. The potential drop at the PEO-LLZO interface is evaluated using the junction potential theory. Using experimental data from the literature, the model estimates the ionic conductivity, effective transference number, and mechanical stiffness of the CEs. While the mechanical stiffness improves with increasing volume fraction of LLZO, the impact on conductivity and transference number depends on interfacial resistance at the interface. Finally, the study reports CE’s potential to enhance Li-ion transport and mechanical properties to inhibit lithium (Li) dendrite growth.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1877696

Alternate ID(s):: OSTI ID: 1905891

Journal Information:: Journal of Solid State Electrochemistry, Journal Name: Journal of Solid State Electrochemistry Journal Issue: 9 Vol. 26; ISSN 1432-8488

Publisher:: Springer Science + Business MediaCopyright Statement

Country of Publication:: Germany

Language:: English

References (63)

Fabrication and Properties of Composites of Poly(ethylene oxide) and Functionalized Carbon Nanotubes Geng, H. Z.; Rosen, R.; Zheng, B. Advanced Materials, Vol. 14, Issue 19 https://doi.org/10.1002/1521-4095(20021002)14:19<1387::AID-ADMA1387>3.0.CO;2-Q	journal	October 2002
Computational Methods for Plasticity de Souza Neto, E. A.; Peri, D.; Owen, D. R. J. John Wiley & Sons, Ltd https://doi.org/10.1002/9780470694626	book	January 2008
Electrochemical Stability of Li ₁₀ GeP ₂ S ₁₂ and Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Han, Fudong; Zhu, Yizhou; He, Xingfeng Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201501590	journal	January 2016
Rational Design of Hierarchical “Ceramic‐in‐Polymer” and “Polymer‐in‐Ceramic” Electrolytes for Dendrite‐Free Solid‐State Batteries Huo, Hanyu; Chen, Yue; Luo, Jing Advanced Energy Materials, Vol. 9, Issue 17 https://doi.org/10.1002/aenm.201804004	journal	March 2019
Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure Krauskopf, Thorben; Mogwitz, Boris; Rosenbach, Carolin Advanced Energy Materials, Vol. 9, Issue 44 https://doi.org/10.1002/aenm.201902568	journal	October 2019
Lithium Ion Pathway within Li ₇ La ₃ Zr ₂ O ₁₂ -Polyethylene Oxide Composite Electrolytes Zheng, Jin; Tang, Mingxue; Hu, Yan-Yan Angewandte Chemie International Edition, Vol. 55, Issue 40 https://doi.org/10.1002/anie.201607539	journal	September 2016
Effect of particle agglomeration and interphase on the glass transition temperature of polymer nanocomposites Qiao, Rui; Deng, Hua; Putz, Karl W. Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 10 https://doi.org/10.1002/polb.22236	journal	April 2011
Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet Ni, Jennifer E.; Case, Eldon D.; Sakamoto, Jeffrey S. Journal of Materials Science, Vol. 47, Issue 23, p. 7978-7985 https://doi.org/10.1007/s10853-012-6687-5	journal	July 2012
Mechanical behavior of Li-ion-conducting crystalline oxide-based solid electrolytes: a brief review Wolfenstine, Jeff; Allen, Jan L.; Sakamoto, Jeff Ionics, Vol. 24, Issue 5 https://doi.org/10.1007/s11581-017-2314-4	journal	November 2017
Some elastic properties of reinforced solids, with special reference to isotropic ones containing spherical inclusions Weng, G. J. International Journal of Engineering Science, Vol. 22, Issue 7 https://doi.org/10.1016/0020-7225(84)90033-8	journal	January 1984
A.c. electrical properties of composite solid electrolytes Nan, Ce-Wen; Smith, Douglas M. Materials Science and Engineering: B, Vol. 10, Issue 2 https://doi.org/10.1016/0921-5107(91)90115-C	journal	October 1991
Enhanced mechanical strength and ionic conductivity of LLZO solid electrolytes by oscillatory pressure sintering Li, Hai-Yan; Huang, Bing; Huang, Zeya Ceramics International, Vol. 45, Issue 14 https://doi.org/10.1016/j.ceramint.2019.05.241	journal	October 2019
Effective properties of composite material based on total strain energy equivalence Wiśniewska, Anna; Hernik, Szymon; Liber-Kneć, Aneta Composites Part B: Engineering, Vol. 166 https://doi.org/10.1016/j.compositesb.2018.11.094	journal	June 2019
A three-dimensional interconnected polymer/ceramic composite as a thin film solid electrolyte Palmer, Max J.; Kalnaus, Sergiy; Dixit, Marm B. Energy Storage Materials, Vol. 26 https://doi.org/10.1016/j.ensm.2019.12.031	journal	April 2020
PEO/LAGP hybrid solid polymer electrolytes for ambient temperature lithium batteries by solvent-free, “one pot” preparation Piana, Giulia; Bella, Federico; Geobaldo, Francesco Journal of Energy Storage, Vol. 26 https://doi.org/10.1016/j.est.2019.100947	journal	December 2019
A theory of plasticity for carbon nanotube reinforced composites Barai, Pallab; Weng, George J. International Journal of Plasticity, Vol. 27, Issue 4 https://doi.org/10.1016/j.ijplas.2010.08.006	journal	April 2011
Design of composite polymer electrolytes for Li ion batteries based on mechanical stability criteria Kalnaus, Sergiy; Sabau, Adrian S.; Tenhaeff, Wyatt E. Journal of Power Sources, Vol. 201 https://doi.org/10.1016/j.jpowsour.2011.11.020	journal	March 2012
Electrochemical performance of a solvent-free hybrid ceramic-polymer electrolyte based on Li 7 La 3 Zr 2 O 12 in P(EO) 15 LiTFSI Keller, Marlou; Appetecchi, Giovanni Battista; Kim, Guk-Tae Journal of Power Sources, Vol. 353 https://doi.org/10.1016/j.jpowsour.2017.04.014	journal	June 2017
Polymer-ceramic composite electrolytes for all-solid-state lithium batteries: Ionic conductivity and chemical interaction enhanced by oxygen vacancy in ceramic nanofibers Yang, Hui; Abdullah, Muhammad; Bright, Joeseph Journal of Power Sources, Vol. 495 https://doi.org/10.1016/j.jpowsour.2021.229796	journal	May 2021
Lithium Dendrite in All-Solid-State Batteries: Growth Mechanisms, Suppression Strategies, and Characterizations Cao, Daxian; Sun, Xiao; Li, Qiang Matter, Vol. 3, Issue 1 https://doi.org/10.1016/j.matt.2020.03.015	journal	July 2020
Flexible and ion-conducting membrane electrolytes for solid-state lithium batteries: Dispersion of garnet nanoparticles in insulating polyethylene oxide Zhang, Jingxian; Zhao, Ning; Zhang, Miao Nano Energy, Vol. 28 https://doi.org/10.1016/j.nanoen.2016.09.002	journal	October 2016
Recent advances in all-solid-state rechargeable lithium batteries Sun, Chunwen; Liu, Jin; Gong, Yudong Nano Energy, Vol. 33 https://doi.org/10.1016/j.nanoen.2017.01.028	journal	March 2017
Particles in composite polymer electrolyte for solid-state lithium batteries: A review Meng, Nan; Zhu, Xiaogang; Lian, Fang Particuology, Vol. 60 https://doi.org/10.1016/j.partic.2021.04.002	journal	January 2022
Electrochemical properties of a ceramic-polymer-composite-solid electrolyte for Li-ion batteries Lee, Seoung Soo; Lim, Young Jun; Kim, Hyun Woo Solid State Ionics, Vol. 284 https://doi.org/10.1016/j.ssi.2015.11.020	journal	January 2016
Microstructure and Pressure-Driven Electrodeposition Stability in Solid-State Batteries Verma, Ankit; Kawakami, Hiroki; Wada, Hiroyuki Cell Reports Physical Science, Vol. 2, Issue 1 https://doi.org/10.1016/j.xcrp.2020.100301	journal	January 2021
Diffusion and Reactions in Fractals and Disordered Systems ben-Avraham, Daniel; Havlin, Shlomo Cambridge University Press https://doi.org/10.1017/CBO9780511605826	book	January 2010
Investigating the Calcination and Sintering of Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling Barai, Pallab; Fister, Timothy; Liang, Yujia Chemistry of Materials, Vol. 33, Issue 12 https://doi.org/10.1021/acs.chemmater.0c04393	journal	June 2021
Optimization of Block Copolymer Electrolytes for Lithium Metal Batteries Devaux, Didier; Glé, David; Phan, Trang N. T. Chemistry of Materials, Vol. 27, Issue 13 https://doi.org/10.1021/acs.chemmater.5b01273	journal	June 2015
Elastic Properties of the Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03854	journal	December 2015
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
Interfacial Stability of Li Metal–Solid Electrolyte Elucidated via in Situ Electron Microscopy Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo Nano Letters, Vol. 16, Issue 11 https://doi.org/10.1021/acs.nanolett.6b03223	journal	October 2016
Garnet–Polymer Composite Electrolytes: New Insights on Local Li-Ion Dynamics and Electrodeposition Stability with Li Metal Anodes Zagórski, Jakub; López del Amo, Juan Miguel; Cordill, Megan J. ACS Applied Energy Materials, Vol. 2, Issue 3 https://doi.org/10.1021/acsaem.8b01850	journal	January 2019
Unveiling Interfacial Li-Ion Dynamics in Li ₇ La ₃ Zr ₂ O ₁₂ /PEO(LiTFSI) Composite Polymer-Ceramic Solid Electrolytes for All-Solid-State Lithium Batteries Bonilla, Mauricio R.; García Daza, Fabián A.; Ranque, Pierre ACS Applied Materials & Interfaces, Vol. 13, Issue 26 https://doi.org/10.1021/acsami.1c07029	journal	June 2021
Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique ACS Applied Materials & Interfaces, Vol. 7, Issue 32 https://doi.org/10.1021/acsami.5b02528	journal	August 2015
Ionic Conduction in Composite Polymer Electrolytes: Case of PEO:Ga-LLZO Composites Li, Zhuo; Huang, He-Ming; Zhu, Jia-Kun ACS Applied Materials & Interfaces, Vol. 11, Issue 1 https://doi.org/10.1021/acsami.8b17279	journal	December 2018
Improving Ionic Conductivity with Bimodal-Sized Li ₇ La ₃ Zr ₂ O ₁₂ Fillers for Composite Polymer Electrolytes Sun, Yan; Zhan, Xiaowen; Hu, Jiazhi ACS Applied Materials & Interfaces, Vol. 11, Issue 13 https://doi.org/10.1021/acsami.8b21770	journal	March 2019
Properties of the Interphase Formed between Argyrodite-Type Li ₆ PS ₅ Cl and Polymer-Based PEO ₁₀ :LiTFSI Simon, Fabian J.; Hanauer, Matthias; Henss, Anja ACS Applied Materials & Interfaces, Vol. 11, Issue 45 https://doi.org/10.1021/acsami.9b14506	journal	October 2019
Promising Routes to a High Li ⁺ Transference Number Electrolyte for Lithium Ion Batteries Diederichsen, Kyle M.; McShane, Eric J.; McCloskey, Bryan D. ACS Energy Letters, Vol. 2, Issue 11 https://doi.org/10.1021/acsenergylett.7b00792	journal	October 2017
Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface Chen, X. Chelsea; Liu, Xiaoming; Samuthira Pandian, Amaresh ACS Energy Letters, Vol. 4, Issue 5 https://doi.org/10.1021/acsenergylett.9b00495	journal	April 2019
Li ₂ CO ₃ : A Critical Issue for Developing Solid Garnet Batteries Huo, Hanyu; Luo, Jing; Thangadurai, Venkataraman ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02401	journal	November 2019
Synergistic Coupling between Li _6.75 La ₃ Zr _1.75 Ta _0.25 O ₁₂ and Poly(vinylidene fluoride) Induces High Ionic Conductivity, Mechanical Strength, and Thermal Stability of Solid Composite Electrolytes Zhang, Xue; Liu, Ting; Zhang, Shuofeng Journal of the American Chemical Society, Vol. 139, Issue 39 https://doi.org/10.1021/jacs.7b06364	journal	September 2017
The Influence of Inert Oxide Fillers on Poly(ethylene oxide) and Amorphous Poly(ethylene oxide) Based Polymer Electrolytes ^† Johansson, Patrik; Ratner, Mark A.; Shriver, Duward F. The Journal of Physical Chemistry B, Vol. 105, Issue 37 https://doi.org/10.1021/jp010868r	journal	September 2001
Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid Nature Materials, Vol. 12, Issue 5 https://doi.org/10.1038/Nmat3602	journal	March 2013
Publisher Correction: High-energy long-cycling all-solid-state lithium metal batteries enabled by silver–carbon composite anodes Lee, Yong-Gun; Fujiki, Satoshi; Jung, Changhoon Nature Energy, Vol. 5, Issue 4 https://doi.org/10.1038/s41560-020-0604-y	journal	March 2020
Correlation of the average hopping length to the ion conductivity and ion diffusivity obtained from the space charge polarization in solid polymer electrolytes Roy, Anirban; Dutta, Bula; Bhattacharya, Subhratanu RSC Advances, Vol. 6, Issue 70 https://doi.org/10.1039/c6ra09529a	journal	January 2016
Lithium dendrite growth mechanisms in polymer electrolytes and prevention strategies Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat Physical Chemistry Chemical Physics, Vol. 19, Issue 31 https://doi.org/10.1039/c7cp03304d	journal	January 2017
Hybrid electrolytes with 3D bicontinuous ordered ceramic and polymer microchannels for all-solid-state batteries Zekoll, Stefanie; Marriner-Edwards, Cassian; Hekselman, A. K. Ola Energy & Environmental Science, Vol. 11, Issue 1 https://doi.org/10.1039/c7ee02723k	journal	January 2018
Nanothin film conductivity measurements reveal interfacial influence on ion transport in polymer electrolytes Dong, Ban Xuan; Bennington, Peter; Kambe, Yu Molecular Systems Design & Engineering, Vol. 4, Issue 3 https://doi.org/10.1039/c9me00011a	journal	January 2019
Visualizing percolation and ion transport in hybrid solid electrolytes for Li–metal batteries Zaman, Wahid; Hortance, Nicholas; Dixit, Marm B. Journal of Materials Chemistry A, Vol. 7, Issue 41 https://doi.org/10.1039/c9ta05118j	journal	January 2019
A review of composite solid-state electrolytes for lithium batteries: fundamentals, key materials and advanced structures Zheng, Yun; Yao, Yuze; Ou, Jiahua Chemical Society Reviews, Vol. 49, Issue 23 https://doi.org/10.1039/d0cs00305k	journal	January 2020
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 152, Issue 2 https://doi.org/10.1149/1.1850854	journal	January 2005
Influence of the Processing on the Ionic Conductivity of Solid-State Hybrid Electrolytes Based on Glass-Ceramic Particles Dispersed in PEO with LiTFSI Samsinger, R. F.; Schopf, S. O.; Schuhmacher, J. Journal of The Electrochemical Society, Vol. 167, Issue 12 https://doi.org/10.1149/1945-7111/abb37f	journal	September 2020
Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode Harry, Katherine J.; Higa, Kenneth; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.0191610jes	journal	January 2016
Microstructure Evolution in Lithium-Ion Battery Electrode Processing Liu, Zhixiao; Mukherjee, Partha P. Journal of The Electrochemical Society, Vol. 161, Issue 8 https://doi.org/10.1149/2.026408jes	journal	January 2014
Impact of External Pressure and Electrolyte Transport Properties on Lithium Dendrite Growth Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 165, Issue 11 https://doi.org/10.1149/2.0651811jes	journal	January 2018
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions Pesko, Danielle M.; Feng, Zhange; Sawhney, Simar Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0921813jes	journal	January 2018
Nanocomposites of Titanium Dioxide and Polystyrene-Poly(ethylene oxide) Block Copolymer as Solid-State Electrolytes for Lithium Metal Batteries Gurevitch, Inna; Buonsanti, Raffaella; Teran, Alexander A. Journal of The Electrochemical Society, Vol. 160, Issue 9 https://doi.org/10.1149/2.117309jes	journal	January 2013
Free-Standing PEO/LiTFSI/LAGP Composite Electrolyte Membranes for Applications to Flexible Solid-State Lithium-Based Batteries Lee, Jeremy; Howell, Thomas; Rottmayer, Michael Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.1321902jes	journal	January 2019
Newman and Balsara on Electrochemical Systems Fourth Edition Chaves, Frances The Electrochemical Society Interface, Vol. 30, Issue 1 https://doi.org/10.1149/2.F01211IF	journal	March 2021
Controlling Ionic Transport through the PEO-LiTFSI/LLZTO Interface Gupta, Arushi; Sakamoto, Jeff The Electrochemical Society Interface, Vol. 28, Issue 2 https://doi.org/10.1149/2.F06192if	journal	January 2019
Composite modeling for the effective elastic properties of semicrystalline polymers Ahzi, Said; Bahlouli, Nadia; Makradi, Ahmed Journal of Mechanics of Materials and Structures, Vol. 2, Issue 1 https://doi.org/10.2140/jomms.2007.2.1	journal	January 2007
Review on Polymer-Based Composite Electrolytes for Lithium Batteries Yao, Penghui; Yu, Haobin; Ding, Zhiyu Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00522	journal	August 2019
A Generalized Approach for Evaluating the Mechanical Properties of Polymer Nanocomposites Reinforced with Spherical Fillers Martinez-Garcia, Julio Cesar; Serraïma-Ferrer, Alexandre; Lopeandía-Fernández, Aitor Nanomaterials, Vol. 11, Issue 4 https://doi.org/10.3390/nano11040830	journal	March 2021

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